EP0321208A1 - Abwehr von Vögeln - Google Patents

Abwehr von Vögeln Download PDF

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Publication number
EP0321208A1
EP0321208A1 EP88311823A EP88311823A EP0321208A1 EP 0321208 A1 EP0321208 A1 EP 0321208A1 EP 88311823 A EP88311823 A EP 88311823A EP 88311823 A EP88311823 A EP 88311823A EP 0321208 A1 EP0321208 A1 EP 0321208A1
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Prior art keywords
hydrogen
alkyl
separately selected
alkyl groups
carbamoyl
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French (fr)
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EP0321208B1 (de
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Peter William Greig-Smith
Michael Frank Wilson
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BTG International Ltd
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National Research Development Corp UK
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/04—Oxygen or sulfur attached to an aliphatic side-chain of a carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aliphatically bound aldehyde or keto groups, or thio analogues thereof; Derivatives thereof, e.g. acetals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/34—Nitriles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system

Definitions

  • This invention relates to the control of birds and in particular to compounds of use as avian repellents.
  • the present invention has developed from an investigation of a group of relatively simple synthetic compounds, some of which contain phenolic groups and many of which do not, and which as far as we are aware have never been identified as occurring in fruit buds. This investigation has led to the discovery of a range of compounds which exhibit varying levels of avian repellent activity.
  • the present invention comprises the use as an avian repellent of a compound of formula (I) wherein X1 and X5 are each separately selected from hydrogen and C1 ⁇ 4 alkyl, halogeno and halogeno-substituted C1 ⁇ 4 alkyl groups; X2, X3 and X4 are each separately selected from hydrogen and C1 ⁇ 4 alkyl, hydroxy, C1 ⁇ 4 alkoxy and phenoxy groups; R1 and R2 are each separately selected from hydrogen and C1 ⁇ 4 alkyl groups; R3 and R4 are each hydrogen or together constitute the second bond of a carbon-carbon double bond joining -CR1R3- and -CR2R4-; and Y is hydroxymethyl, formyl, cyano, carbamoyl, carbamoyl N-substituted by one or two of the same or different C1 ⁇ 4 alkyl groups, carboxy or a carboxylic ester or carboxylate salt.
  • X1 and X5 are each separately selected from hydrogen
  • the compounds (I) may exist in various stereoisomeric forms but in the case of the compounds in which R3 and R4 represent the second bond of a carbon-carbon double bond, i.e. cinnamic acid and its derivatives and analogues, the preference is for the commonly occurring trans isomeric form rather than the cis isomeric form.
  • X1 and X5 are conveniently each separately selected from hydrogen or to a lesser extent from C1 ⁇ 4 alkyl, or alternatively from a halogeno group such as fluoro, chloro, bromo or iodo, or to a lesser extent additionally from a halogeno-substituted methyl group, for example trifluoromethyl.
  • X2, X3 and X4 are conveniently each separately selected from hydrogen and C1 ⁇ 4 alkoxy groups, especially ethoxy and particularly methoxy, or to a lesser extent additionally from phenoxy and also hydroxy.
  • R1 and R2 these are preferably each separately selected from hydrogen, methyl and ethyl, especially from methyl and particularly from hydrogen.
  • each of R1 and R2 is hydrogen or one is hydrogen, preferably R2, and the other is a C1 ⁇ 4 alkyl group, preferably methyl.
  • R3 and R4 preferably together constitute the second bond of a double bond.
  • this is preferably a formyl group or more especially a carboxy group or an ester or salt thereof, and particularly a carbamoyl group substituted by two or especially one C1 ⁇ 4 alkyl group, for example ethyl or particularly methyl, or especially an unsubstituted carbamoyl group.
  • Esters may conveniently be formed with aliphatic or aromatic alcohols, particularly those containing a C1-C24 aliphatic hydrocarbon group, for example an alkyl or alkenyl group, or an aromatic hydrocarbon group such as an unsubstituted or substituted napthyl or particularly phenyl group, whilst salts may be formed with various organic or inorganic bases, for example an alkali metal hydroxide such as sodium hydroxide, a quaternary ammonium hydroxide or an amine such as 2-amino-2-hydroxymethyl propane 1,3-diol (tris).
  • alkali metal hydroxide such as sodium hydroxide
  • a quaternary ammonium hydroxide such as 2-amino-2-hydroxymethyl propane 1,3-diol (tris).
  • the use of such derivatives which are conveniently of physiologically acceptable form, may be of value in formulation.
  • esters containing the larger aliphatic hydrocarbon groups will be less water soluble than the free acid and many salts
  • Compounds of some particular interest have X2 and X4 which are each separately a C1 ⁇ 4 alkoxy group, for example an ethoxy or especially a methoxy group, conveniently together with groups X1, X3 and X5 in which X1 and X5 are each hydrogen and X3 is C1 ⁇ 4 alkoxy, for example ethoxy or especially methoxy or preferably which are each hydrogen.
  • X1, X2, X3, X4 and X5 which are each hydrogen.
  • Such compounds of particular interest may conveniently have R3 and R4 which constitute a second bond of a carbon-carbon double bond, particularly together with R1 and R2 which are each hydrogen; Y especially being either carboxy or to a lesser extent a carboxylic ester or carboxylate salt, or more preferably a carbamoyl group or to a lesser extent an N-substituted carbamoyl group.
  • the present invention relating to the use of the compounds of formula (I) as avian repellents is not limited by any theory as to the mode of action of the repellents.
  • the particular effectiveness of the compounds of formula (1) as avian repellents might lie in their ability to inhibit the biochemical process of enzymatic proteolysis which takes place in the small intestine of the bird we have investigated such inhibition. This inhibition reduces the nutritional quality of foodstuffs ingested by the bird and in turn discourages it from further feeding on a treated crop.
  • the major alkaline serine protease in birds is either chymotrypsin, for example in the quail and starling, or trypsin, for example in the bullfinch and pigeon. It has been found that the relative degree of inhibition of chymotrypsin and trypsin varies between the various compounds (I). If the avian repellent activity of the compounds (I) were based primarily on their enzyme inhibiting ability this finding would have potentially important consequences since to optimise the repellent effect on all birds the use would be indicated of either a compound (I) which is effective against both chymotrypsin and trypsin or of a mixture of compounds (I), one of which is particularly effective against chymotrypsin and another against trypsin.
  • bullfinches are particularly destructive of fruit buds but most other birds cause less damage and can have a beneficial effect through the control they exert upon the insect population. This raises the possibility that it could be advantageous to repel bullfinches selectively, a possible approach being the use of a compound (I) showing a high degree of inhibition of trypsin but a low level of inhibition of chymotrypsin.
  • compounds (I) in which X1 and X5 are hydrogen and one or more of X2, X3 and X4 is a hydroxy or alkoxy group, for example a methoxy group generally tend to be worse inhibitors of trypsin than the corresponding ring unsubstituted compound.
  • cinnamic acid may conveniently be prepared by a Perkin reaction from benzaldehyde, for example using acetic acid and anhydrous sodium or potassium acetate, and ring substituted derivatives thereof may be prepared similarly from a substituted benzaldehyde.
  • cinnamamide may conveniently be prepared by the reaction of cinnamoyl chloride (which can be prepared from cinnamic acid by reaction with thionyl chloride, phosphorus trichloride or phosphorus pentachloride) with ammonia or by forming the ammonium salt of cinnamic acid by reaction with ammonia and then heating this to give cinnamamide, ring substituted derivatives being prepared by the use of a substituted cinnamic acid and N-subtituted derivatives by the use of an appropriate amine in place of ammonia.
  • the compound dihydrocinnamic acid in which R3 and R4 are each hydrogen may be prepared by the hydrogenation of the carbon-carbon double bond of cinnamic acid, for example in the presence of a nickel catalyst. Ring substituted derivatives may be prepared similarly with protection of the substituents where necessary, and compounds containing a group Y other than carboxy may either be prepared from the corresponding saturated compound in the same way with protection of the group Y where necessary or by modification of the carboxy group of the corresponding dihydrocinnamic acid.
  • the compounds (I) are of interest in repelling a wide variety of birds irrespective of whether their main alkaline serine protease is chymotrypsin or trypsin, although the compounds are of particular interest in the case of some birds which present particular problems such as pigeons and bullfinches, and also starlings and sparrows, as well as geese, for example the Brent goose or the Canada goose ( Branta canadensis , the red-winged blackbird ( Agelius phoeniceus ) and the brown-headed cowbird ( Molothrus ater ) particularly in the USA, weaver birds, for example Pavea quelea , particularly in Africa, and the Indian house crow particularly in India and Africa.
  • a particular area of use of the compounds is in a horticultural context for the avoidance of damage to developing buds, particularly during the dormant season, especially fruit buds, for example of the top fruits apples, pears, plums, etc., to developing top fruit, particularly cherries, and to formed soft fruit prior to harvest, for example raspberries, strawberries, loganberries, blackberries, blackcurrants, gooseberries, etc.
  • Other applications include protection of the seeds of growing crops, particularly sunflowers and oil seed rape.
  • the compounds (I) may be used for the protection of any plant material and that this may be in embryo, growing or harvested form, including the forms of seeds, seedlings, buds, leaves and other vegetative parts, and fruit.
  • the compounds (I) are also of potential interest in any context where it is desirable to prevent bird damage, for example in the protection of structures and particularly electric cables from nibbling by birds.
  • the present invention thus includes a method for the treatment of a growing or harvested plant material, or any other substance which is exposed to birds, which comprises applying to that material or substance a compound of formula (I) as defined hereinbefore.
  • the invention further extends to such plant material, for example fruit and seeds, or substance when so treated.
  • the compounds (I) may be formulated for application with various suitable types of diluent or carrier, particularly for agricultural/horticultural purposes, including aqueous formulations, oily formulations, etc.
  • aqueous formulations particularly for agricultural/horticultural purposes
  • One suitable type of formulation involves the use of aqueous acetone as a diluent especially with a higher proportion of water than acetone, such as 60-90% water:40-10% acetone (by volume), for example 80% water: 20% acetone (by volume).
  • a variety of alternative diluents or carriers which are acceptable for application onto crops may conveniently be used to provide a solution, suspension, emulsion or powder containing the compound (I).
  • compositions for treating harvested seeds solid carriers, for example one of various clays such as kaolin and bentonite, may conveniently be used to provide powder formulations, together with an emulsifying agent where appropriate.
  • emulsifying agents for enhancing both the preparation of the composition and its application to the plant or other material.
  • Suitable emulsifying agents are particularly the non-ionic surface active agents and especially those based on a polyether structure, for example polyoxyethylene stearate and nonylphenylpolyoxyethanol.
  • additional component which may be considered for inclusion in the composition include various colouring agents, for example the commercially available materials Rhoplex AC-33, Trition AE and Acronal 4D (BASF), since birds are repelled by unfamiliar or aversive visual clues, agents which enhance adhesion of the compostiion to the material substance to which it is applied, for example Sky Blue and other commercially available food colourings, as well as insecticides, fungicides, etc., as appropriate.
  • composition may contain more than one compound (I), for example one which is particularly effective in inhibiting chymotrypsin and another which is particularly effective in inhibiting trypsin, since this is often a more convenient approach than applying two such compounds separately.
  • Treatment will be applied at an appropriate time, for example either in advance or in response to bird attack.
  • such treatment is commonly applied during the dormant season, i.e. the late autumn, winter and early spring, for example from November to February in the United Kingdom.
  • the application of the composition containing the compounds (I) may conveniently be effected by standard means, and often by spraying, for example by the use of drum sprayers in orchards and may be repeated as necessary to maintain the desired level of control.
  • Further general information concerning the formulation and use of avian repellents is provided by data on the use of existing repellents such as anthraquinone, thiram, aluminium ammonium sulphate, quassia extract and particularly methiocarb outside the United Kingdom.
  • the rate of application of the compounds will depend both upon the particular compound (I) which is being used and upon the nature and location of the substance being treated. However, by way of guidance it may be stated that for the treatment of growing crops an application rate of 0.1 to 100, particularly 1 to 10 kilograms per hectare, of the compound (I) is often appropriate, the aim being to use the minimum effective quantity which may, for example, be 5 kilograms per hectare or a lesser amount as indicated. For the treatment of harvested crops, for example seeds, an application rate of 0.01 to 1, particularly 0.05 to 0.5% w/w, of the compound (I) to treated material is often appropriate. Once again, the aim is to use the minimum effective quantity which may, for example, be 0.1% w/w or a lesser amount as indicated.
  • the birds (five week old female Japanese quail, wild, trapped bullfinches or feral pigeons) were sacrificed and the small intestine and gizzard were removed and immersed in liquid nitrogen for 5 minutes. The frozen gizzard and small intestine tissues were then lyophilised separately for 24 hours, ground to a fine powder in a hammer mill and stored, dessicated at -20°C, until required for analysis.
  • Dried avian gut tissue powder (500 mg) was extracted for 30 minutes in the appropriate buffer [acid protease assay: 10 mM HCl (10 ml)/alkaline protease assay: 100 mM Tris-HCl (Tris is an abbreviation for 2-amino-2-hydroxymethylpropane 1,3-diol) buffer of pH 7.0 (10 ml)] at ambient temperature.
  • the extract was centrifuged at 22,000 x g for 30 minutes at 4°C and the resultant supernatant removed for subsequent assays.
  • Acid protease activity was determined by the method of Rick and Fritsh, Methods of Enzymatic Digestion, l974, 2nd edition, page 1046 (edited by Bergmeyer, Academic Press Inc., London), using a haemoglobin substrate. The reaction was carried out in 4 ml plastic disposable test tubes containing the haemoglobin substrate [bovine haemoglobin lyophilised powder, 200 mg/ml in 10 mM HCl (i.e. 10 mM aqueous hydrochloric acid) (1 ml)] and 10 mM HCl (400 ⁇ l).
  • the reaction was started by the addition of gut extract (20 ⁇ l) and stopped after 10 minutes by the addition of 5% (w/v) trichloroacetic acid (2 ml).
  • the tubes were mixed and centrifuged at 4000 x g for 20 minutes.
  • An aliquot of the resultant supernatant (1 ml) was added to 0.5M NaOH (2 ml) in a plastic cuvette (1 x 1 x 4 cm3).
  • Folin-Ciocalteu reagent diluted 1:3 v/v with distilled water (0.6 ml of diluted reagent) was added and the absorbance at 691 nm determined against a reagent blank after 9 minutes. All determinations were carried out in triplicate.
  • Alkaline protease activity was determined using a denatured haemoglobin substrate. This was produced by mixing haemoglobin (0.5 mg) with distilled water, (10 ml), urea (9 g) and 1M NaOH (2 ml) and leaving for 1 hour. Calcium chloride (5% w/v, 1.1 ml) and boric acid solution (1M + 7 mM NaCl, 2.5 ml) were then added, the pH adjusted to 7.5 with HCl, the volume made up to 25 ml with water and the solution centrifuged at 4,000 x g for 20 minutes. The assay was carried out using this substrate as described for the assay of acid protease activity with the exception that 100 mM Tris HCl buffer of pH 7.5 was used instead of 10 mM HCl as the reaction medium.
  • the alimentary canal has substantial acid and alkaline serine protease activity but the former will be inactive at the pH of about 7.0 and, in the gizzard, the slightly higher acid serine protease activity will be that prevailing as the alkaline serine protease activity will not be evident at the pH of about 2.0.
  • Dried avian intestine powder (500 mg) was extracted for 30 minutes in 1 mM HC1 (5 ml). The extract was centrifuged at 22,000 x g for 30 minutes at 4°C. The resultant supernatant was applied to a column of Sephadex G-50, medium grade (360 mm x 15 mm) and eluted with 0.5 mM HCl at 0.7 ml/min. Fractions (3.5 ml) were collected and tested for the presence of protein by determining their absorbance at 280 nm. The proteinaceous fractions were bulked and concentrated by passing them through an ultrafiltration unit (YM 30 filter). The concentrate was collected and kept at 4°C throughout its use.
  • YM 30 filter ultrafiltration unit
  • N-Acetyl-L-tyrosine ethyl ester (ATEE) assay chymotrypsin
  • the substrate was prepared by dissolving ATEE (10 mg) in Tris-HCl buffer of pH 7.5 containing 30% (v/v) of methanol (25 ml).
  • the quail intestine protease activity was partially purified as described above prior to testing for chymotrypsin activity.
  • the reaction was carried out in a quartz cuvette (1 x 0.25 x 1 cm3) containing substrate (1 ml) and 100 mM Tris-HCl buffer (200 ⁇ l).
  • the reaction was started by the addition of the partially purified intestine protease (200 ⁇ l) and followed bv the decrease in absorbance at 237 nm over a 5 minute period. All determinations were carried out in triplicate against a reagent blank.
  • the substrate was prepared bv dissolving BAEE (10 mg) in a mixture of 50 mM Tris-HCl buffer of pH 7.5 (24 ml) and 5% (w/v) calcium chloride solution (1 ml).
  • the bullfinch intestine protease activity was partially purified as described above prior to testing for trypsin activity.
  • the reaction was carried out in a quartz cuvette (1 x 0.25 x 1 cm3) containing substrate (1 ml) and 50 mM Tris-HCl buffer (200 ⁇ l).
  • the reaction was started by the addition of the partially purified intestine protease 1200 ⁇ l) and followed by the decrease in absorbance at 253 nm over a 7 minute period. All determinations were carried out in triplicate against a reagent blank.
  • TAME N-p-Toluenesulfonyl-L-arginine methyl ester
  • the substrate was prepared by dissolving TAME (19 mg) in a mixture of 100 mM Tris-HCl buffer of pH 7.5 (50 ml) and 5% (w/v) calcium chloride solution (2 ml).
  • the pigeon intestine protease was partially purified as described above prior to testing for trypsin activity.
  • the reaction was carried out in a quartz cuvette (1 x 0.25 x 1 cm3) containing substrate (3 ml) and 100 mM Tris-HCl buffer pH 7.5 (100 ⁇ l).
  • the reaction was started by the addition of the partially purified intestine protease (100 ⁇ l) and followed by the decrease in absorbance at 247 nm over a 5 minute period.
  • FIG. 2a The results of the determinations of chymotrypsin and trypsin activity in the small intestine are shown in Figure 2a for the Japanese quail and in Figure 2b for the bullfinch.
  • A relates to chymotrypsin (ATEE assay) and B to trypsin (BAEE assay). It will be seen that chymotrypsin is responsible for most of the detectable quail intestinal protease activity but that trypsin is responsible for most of the detectable bullfinch intestinal protease activity. In the case of the pigeon, chymotrypsin was substantially absent so that essentially all of the intestinal protease activity was due to trypsin.
  • the ATEE, BAEE and TAME assay procedures were carried out as described above but adding to the substrate one of a series of compounds (I) or one of an alternative group of compounds to provide a comparison with the compounds (I), the compound either (a) in the ATEE and BAEE assays being made up to a concentration of 1 x 10 ⁇ 5M by addition in 100 mM Tris-HCl buffer of pH 7.5 (100 ⁇ l) which replaced the 200 ⁇ l of this buffer mixed in the cuvette with the substrate, or (b) in the TAME assay being made up to a concentration of 60 ⁇ g/ml by addition at 2 mg/ml in 100 mM Tris-HCl buffer of pH 7.5 (100 ⁇ l) which is added to the 100 ⁇ l of this buffer already present. In both the chymotrypsin and the trypsin assays a control was however carried out using the 200 ⁇ l of buffer containing no added compound.
  • Example 2 Feeding trials with Japanese quail
  • TSC standard turkey starter crumbs
  • the treated TSC was prepared in each case by dissolving/­suspending the compound or compounds in diethyl ether (1500 ml) and mixing this with TSC (2000 g) at 0.25% or 0.5% w/w concentration compound/TSC in an industrial food mixer for 1 hour to evaporate off the diethyl ether and produce a homogeneous mixture.
  • the control was prepared by mixing TSC (2000 g) with diethyl ether for 1 hour in an industrial food mixer. The amount of each diet consumed and the weight gain of the birds was recorded on a daily basis for a period of 14 days. The trial was carried out in duplicate.
  • Example 3 Feeding trials with feral pigeons
  • Feral pigeons were transferred from a communal outdoor aviary to individual cages and maintained on a 10 hour light - 14 hour dark cycle. Birds were gradually weaned away from their normal diet of maize, wheat and maple peas to a standard laboratory diet of turkey starter pellets. All birds lost weight during the first few days as they adjusted to their new conditions. Most began to regain weight after 3 or 4 days. Some birds could not adapt, continued to lose weight and were removed from the experiment. After about two to three weeks the bird weights were more or less stable and the trials were commenced.
  • the birds were tested with a range of compounds (I) and also with sucrose octaacetate and dimethyl anthranilate which are known to be offensive to birds.
  • the compounds for testing were each dissolved in an 80/20 v/v acetone/water mixture and sprayed onto turkey starter pellets to give a 0.5% w/w compound/pellet concentration.
  • the pellets were oven dried and then left to absorb atmospheric moisture.
  • the control food was sprayed with the same volume of acetone/water mixture.
  • a group of 35 feral pigeons was caged individually for the trials which used eight compounds of formula (I) together with sucrose octaacetate and dimethyl anthranilate, both of which are substances which are known to be avian repellents.
  • Each bird was subjected to treatment with each compound in a random order subject to the limitation of a latin square design.
  • Each treatment was presented to the birds in no-choice and two-choice conditions.
  • the no-choice phase lasted 3 days, during which a bird was presented with a single bowl containing 120 g of treated food.
  • Each bird was weighed before and after the no-choice phase, as was the amount of food remaining.
  • Cinnamic acid and 3,4-dihydroxycinnamic acid were tested in the field for their ability to deter bullfinches from feeding on developing buds on pear trees.
  • Levels of damage were monitored in two commercial orchards from early February to April by regularly scoring the proportions of buds pecked bv bullfinches in a standard sample of 50 buds on each tree. When damage had reached a moderate level, 20 trees in each orchard were chosen for experimental spraying, these trees being in a band several metres from the edge of the orchard where approximately 10-20% of the buds were affected. A part of each tree containing about 250 buds was sprayed, and subsequent damage was counted and compared to damage on (a) another part of the same tree and (b) an adjacent, unsprayed tree.

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  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Seasonings (AREA)
  • Catching Or Destruction (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Saccharide Compounds (AREA)
  • Housing For Livestock And Birds (AREA)
  • Ultra Sonic Daignosis Equipment (AREA)
  • Electrotherapy Devices (AREA)
EP88311823A 1987-12-14 1988-12-14 Abwehr von Vögeln Expired - Lifetime EP0321208B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88311823T ATE64815T1 (de) 1987-12-14 1988-12-14 Abwehr von voegeln.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8729109 1987-12-14
GB878729109A GB8729109D0 (en) 1987-12-14 1987-12-14 Improvements in/relating to avian control

Publications (2)

Publication Number Publication Date
EP0321208A1 true EP0321208A1 (de) 1989-06-21
EP0321208B1 EP0321208B1 (de) 1991-07-03

Family

ID=10628457

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EP88311823A Expired - Lifetime EP0321208B1 (de) 1987-12-14 1988-12-14 Abwehr von Vögeln

Country Status (21)

Country Link
EP (1) EP0321208B1 (de)
JP (1) JP2769216B2 (de)
KR (1) KR970005231B1 (de)
CN (1) CN1030681C (de)
AT (1) ATE64815T1 (de)
CA (1) CA1336392C (de)
CZ (1) CZ282210B6 (de)
DD (1) DD286099A5 (de)
DE (1) DE3863538D1 (de)
EG (1) EG18985A (de)
ES (1) ES2022992B3 (de)
GB (2) GB8729109D0 (de)
GR (1) GR3002253T3 (de)
HU (1) HU208223B (de)
PL (1) PL159564B1 (de)
PT (1) PT89219B (de)
RU (1) RU1837766C (de)
SK (1) SK827888A3 (de)
TR (1) TR24930A (de)
WO (1) WO1989005580A1 (de)
ZW (1) ZW17888A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1585745A4 (de) * 2002-12-24 2008-07-09 Trillium Therapeutics Inc Verbindungen und zusammensetzungen für fc-rezeptormodulation

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8829166D0 (en) * 1988-12-14 1989-01-25 Greig Smith Peter W Improvements in or relating to rodent control
US5839224A (en) * 1994-12-30 1998-11-24 Proguard, Inc. Aromatic aldehydes as insecticides and for killing arachnids
US6750256B1 (en) 1994-12-30 2004-06-15 Proguard, Inc. Use of aromatic aldehydes as insecticides
PL209602B1 (pl) 2005-10-20 2011-09-30 Inst Chemii Bioorg Pan Sposób otrzymywania amidu kwasu 3-(4-hydroksyfenylo)propanowego
US8457114B2 (en) 2009-09-28 2013-06-04 Telefonaktiebolaget Lm Ericsson (Publ) Method to optimize call establishment in mobile satellite communication systems
US8410176B2 (en) 2009-12-29 2013-04-02 Mapi Pharma Ltd. Intermediate compounds and processes for the preparation of tapentadol and related compounds
CN103548865A (zh) * 2012-08-27 2014-02-05 安徽爱戈德生物科技有限公司 一种驱鸟组合物及其液体制剂及其制备方法
CN104824031A (zh) * 2014-02-11 2015-08-12 吕夫成 一种无公害驱鸟拌种剂及其制备方法
CN104255791B (zh) * 2014-09-23 2017-06-06 中宁化集团有限公司 一种鸟兽驱避物及使用方法
JP6347355B2 (ja) 2016-12-21 2018-06-27 大阪ウイントン株式会社 鳥類忌避塗料
CN114938810A (zh) * 2022-06-27 2022-08-26 赤天化科技集团有限公司 适合无人飞防的含噻呋酰胺和嘧菌酯的杀菌组合物

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2390249A (en) * 1945-09-14 1945-12-04 Stanley A Hall Insect-repellent composition
US2967128A (en) * 1957-06-06 1961-01-03 S B Penick And Company Inc Bird repellent

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1018308A (en) * 1963-03-27 1966-01-26 Shell Res Ltd Novel dichlorophenyl-substituted amides,thioamides,imidates and amidines,and herbicidal compositions containing them
ES311043A1 (es) * 1964-04-06 1965-08-16 Lilly Co Eli Un procedimiento para preparar derivados del acido cinamico.
BR8206283A (pt) * 1982-07-06 1984-04-17 Kiyoshi Saotome Processo para protecao de culturas

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2390249A (en) * 1945-09-14 1945-12-04 Stanley A Hall Insect-repellent composition
US2967128A (en) * 1957-06-06 1961-01-03 S B Penick And Company Inc Bird repellent

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 97, no. 6, 9th August 1982, page 336, abstract no. 44321n, Columbus, Ohio, US; & JP-A-82 46 915 (MANYU SEIYAKU K.K.) 17-03-1982 *
CHEMICAL PATENTS INDEX, BASIC ABSTRACTS JOURNAL, section C, week 8705, 1st April 1985, abstract no. 87-032874/05, Derwent Publications Ltd, London, GB; & JP-A-61 289 003 (MIKASA KAGAKU KOGYO K.K.) 19-12-1986 *
IL FARMACO - ED. SC., vol. 28, no. 3, 1973, pages 214-242, Farmaco, Davia, IT; G. PAGANI et al.: "Derivati cinnamici ad azione fitotossica. nota I" *
IL FARMACO - ED. SC., vol. 28, no. 3, 1973, pages 230-242, Farmaco, Davia, IT; G. PAGANI et al.: "Derivati cinnamica ad attivita fitotossica. nota II" *
J. ENVIRON. SCI. HEALTH, part A, vol. A18, no. 4, 1983, pages 493-502, Marcel Dekker, Inc.; E.W. SCHAFER Jr. et al.: "Repellency and toxicity of 55 insect repellents to red-winged blackbirds (Agelaius phoeniceus) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1585745A4 (de) * 2002-12-24 2008-07-09 Trillium Therapeutics Inc Verbindungen und zusammensetzungen für fc-rezeptormodulation
US7910770B2 (en) 2002-12-24 2011-03-22 Trillium Therapeutics Inc. Fc receptor modulating compounds and compositions

Also Published As

Publication number Publication date
SK278915B6 (sk) 1998-04-08
KR970005231B1 (ko) 1997-04-14
HUT57543A (en) 1991-12-30
WO1989005580A1 (en) 1989-06-29
PT89219A (pt) 1989-12-29
ES2022992B3 (es) 1991-12-16
RU1837766C (ru) 1993-08-30
PL159564B1 (pl) 1992-12-31
ATE64815T1 (de) 1991-07-15
CN1030681C (zh) 1996-01-17
CZ282210B6 (cs) 1997-06-11
GR3002253T3 (en) 1992-12-30
DD286099A5 (de) 1991-01-17
JPH02502643A (ja) 1990-08-23
KR900700009A (ko) 1990-08-11
TR24930A (tr) 1992-07-23
PT89219B (pt) 1995-03-01
EP0321208B1 (de) 1991-07-03
ZW17888A1 (en) 1990-01-17
GB8729109D0 (en) 1988-01-27
GB2209943A (en) 1989-06-01
DE3863538D1 (de) 1991-08-08
EG18985A (en) 1994-09-29
GB2209943B (en) 1991-12-11
GB8829167D0 (en) 1989-01-25
CN1035034A (zh) 1989-08-30
CZ827888A3 (en) 1997-03-12
HU208223B (en) 1993-09-28
SK827888A3 (en) 1998-04-08
HU890364D0 (en) 1991-11-28
CA1336392C (en) 1995-07-25
JP2769216B2 (ja) 1998-06-25

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